Optically bleached fibrous material



FIPfiSOQ Patented Aug. 18, 1953 UNITED STATES \OPTICALLY BLEACHED FIBROUS MATERIAL John David Kendall and Douglas James Jim, Ilford, England, assignors t 'llfoltii Limited,

13Claims. 1 This application is ,a continuation-impart of our application No. 137,673, filed January 9, "1950, and now Patent No. 2620282.

This invention relates to a process for the Ilford, England, aBritish company NoDraWing. Application October-2,5, 1951.;Serial In Great Britain January .14,

The following are examples of specific .com pounds which may "be employed according to the present invention;

(1:) -3,.-3-tdimethy1QOXacyanineiodide, M. Pt. sir

improvement of synthetic fibrous materials havz 1 (T i g a basis of organic derivatives of cellulose. iif g ii g g g gz zgfi memo Within this term is to be understood textile ma- (2:) loxac m M Pt terials in the form of filaments, threads, yarns, y woven or knitted iabr'icsmade of cellulose esters (39 j g j 1 did such as cellulose acetate, cellulose propionate, 9 d 'oxacyamne cellulose butyrate and mixed cellulose esters as, (4) ,1 '5 gxggg' oxac 2min by for instance, cellulose acetate-buty-rate and oel- C th lulose,acetate-propionate, or cellulose ethers such i eccmp" e j" as ethyl cellulose and benzyl cellulose. Also inspending cluded are synthetic fibrous materials made of g f g i tgs ggf g g ptoluene any of the foregoing types of cellulose derivatives (5) 223 5 23 2; fi bkig jfig 23;? textile foim, e. g. compacted synthetic l MJPtigzicfdecompl According to the present invention a process g fif gi -E oxacya' for improving synthetic fibrous materials having (7X) ;?9; 32 1 p c. .a basis of or anic derivatives of cellulose and g' 3 a y'moxacyamne particularly forimp-rovingitextiles made of cellu- (8) yaudiwekh i ig i 7 lose acetate, comprises ap l ing thereto 'a small f fig t (M 5653 3 8? qtlmntlty'cf compound of the general formula" (9-) :323'15,:5Htetramethyl .oxacyanine bromide f 0 0 f I (Met. 293 to. .withdecompl).

.(lO) 3135:1555zfi-pentamethyl'oxacyanine ,p-tdl- 5,6 7 e ,uene.sulphonate (M. P. 280 C. with dre- -2o-oH=.o2' I a comp)" wmg/ 3' 4' R9 ,(11) ,3:,3;.5:,61tetramethyl ,oxacyanine p-toluene l N T sulphona't'e '(M. Pt. 314 C. with decomp). R2 (12.) 3,13- dimethyl15 acetamino oxacyanine p- R1 X toluene sulphonate (M. Pt. 283 0. with wherein R1 and R2 are alkyl or oxyalkyl groups, decom v and 8 R10 y s hydrogen atoms, or any (13) 3/:3'dim ethyl ;5-bromoxacyanine p-toluene of them may represent substituted groups such lsulphonatc Pt. 298C. with decomp), as alky-l, :alkoXy, amino and substituted amino (l4) 3.'3.,. 5.5'-tetramethyl oxacyanine p-toluene roups, "or halogen atoms, and Xis an acid radsulphonate, M. :Pt. 269 C. decomp. icle, which compound is colourles i thyl alco- (15) .,3.3- dime thy l F 5 .5'-dimethoxy-oxacyanine holic solutionthe t rm c l l "in-ethyl p-toluene sulphonate, M. Pt. 285 C. with alcoholic solution is meant that a solution of 49 degomp, the comp d in ethyl l l :h n rp i n (16,) 3 ;3- dimethyl-5 methoxy-5-meth-yl oxacymaximum not greater than 4000 A. wine p-toluenesuln The preferred compounds according to this ini mp. vention are those in which the absorption maxi- The cpmpounds f the :foregoing general mum is bGlOW 3900 and Of these the compound ifgr mula ma y be prepared by condensin ,a quater in which some of R3 :to R10 represent lower alkyl :nary saltpf anappropriateZ-methyl benzoxazole oralkoxy groups and the remainderiare hydro cn with a quaternary salt of an appropriate 2-alkylatoms are preferred. The nature of the acid it'hiObBHZGXMOlC-l-Il thepnesenceof a :base such as radicle Xappears to .be of little importance :apart pyridine, Lfrom :its .efieot on the solubility of the corn- 50 The compounds of the foregoing general forpounds. it may he halideor sulphate, :but'from 'mula which are colourless, white or pale yellow the practical standpoint the .p-toluene sulhave been found to possess .astrong [fluorescence p-honates are generally preferred as these have in daylight and a slightly less fluorescence .in usually :a satisfactory degree of solubility in incandescent electric or similar light, and .on t application to cellulose derivative fibrous ,materials they impart such fluorescence to them. The fluorencence varies in colour between violet, pale blue and deep blue. The effect of applying these compounds to the fibrous materials is to impart a degree of brilliance to them which is attractive and useful. Applied to materials which are allegedly white, but of which the whiteness has a slight tinge of yellow or brown, the compounds serve to kill the yellow or brown tinge so that the apparent whiteness of the materials is very appreciably enhanced. This application of the materials is of especial importance, and the present invention is therefore particularly concerned with the application of the compounds to such off-white fibrous cellulose, derivative materials. Applied to dyed cellulose derivative textile materials the compounds have the effect of improving the apparent purity of the colour.

The compounds of the present invention, being salts of organic bases, are more or less readily soluble according to their constitution in polar organic solvents such as lower alcohols, esters and ketones and are sufficiently soluble in water to permit their application to cellulose derivative fibrous materials from aqueous solution. In aqueous solution they exhibit a remarkably nonselective affinity to the various types of fibres referred to above so that they can be applied from very dilute solution without the aid of auxiliary agents and without having to be dispersed in finely divided form.

Very small quantities of the compounds are suificient to achieve the desired improvement in the cellulose derivative fibrous materials. Thus treatment of the materials with one of the said compounds, in water or an organic solvent, at a solution concentration of 1 part in 1000 to 1 part in 1,000,000 is usually satisfactory. In such aqueous concentration they are taken up readily on fibres having a cellulose ester basis, e. g. cellulose acetate.

Optical bleaching agents or brightening agents which function by virtue of their inherent fluorescence are already known for application to fibrous materials. However, the previously known materials, where they have been applicable from aqueous solution, have had a restricted application to such materials as wool and cellulose fibres, and have been virtually useless for application to cellulose ester materials.

It is one of the principal features of the present invention that it provides for the first time optical bleaching agents which can be taken up from aqueous solution on to fibrous materials havin a basis of cellulose esters, and yields by such treatment products which are not only satisfactorily brightened but of which the brightening effect is satisfactorily fast both to light and to washing.

The fact that the compounds of the present invention can be taken up from aqueous solution on to cellulose ester fibres is the more surprising when it is appreciated that the commercial dyeing of these fibres in deep colours can only be satisfactorily achieved by the use of finely dispersed azo dyestuffs. For this reason these fibres could, up to now, only be satisfactorily brightened by the use of fine aqueous dispersions of water-insoluble blue-fluorescing brightening agents. In contrast, the compounds of the present invention can be applied by a much simpler process and they yield products which are not only satisfactorily brightened and which have good fastness to washing, but which have, in particular, a degree of light-fastness greater than 4 that hitherto obtained by the use of any of the usual brightening agents.

Because of their special properties, the compounds of the present invention fill a long-standing gap in the field of the optical bleaching of textiles. Their practical value in the field of treating cellulose ester fibres is remarkable and unexpected, and they present the additional practical advantage that they can be applied to mixed fibres, e. g. mixed fabrics of acetate ilk with other synthetic or natural textile fibres.

The effectiveness of the compounds of this invention varies to some extent, and of those listed above the compounds found most useful are numbers l4, l5 and 16 which have a sufiiciently good solubility in water to make their application from that medium a sound commercial practice.

The compounds of this invention may be applied to cellulose derivative fibrous materials at any stage in the manufacture of such materials. Thus in the production of artificial filaments or fibres by the extrusion of cellulose ester compositions, the oxacyanine compound of this invention may be incorporated in such compositions before extrusion so that they are uniformly dispersed throughout the products.

Alternatively the cellulose derivative fibrous materials may be treated with solutions of the compounds at any stage in the manufacture of the fibrous materials. Thus in the treatment of cellulose derivative textile materials the compounds may be included in any of the liquids commonly employed for dyeing, dressing and the like.

The following examples serve to illustrate the invention but are not to be regarded as limiting it in any way:

Example 1 20 gm. of acetate silk skein are introduced at 50 C. into a dyebath containing 0.01 gm. 3 3 :5:5 :6 :6'-hexamethyloxacyanine p toluene sulphonate in 1000 cc. water. The temperature is raised during 15 minutes to C. and kept at this temperature for a further 15 minutes. The skein is then rinsed with cold water and dried. The yarn so obtained exhibits in daylight a very good brightening effect which is characterised by good light fastness and fastness to washing.

Example 2 30 gm. of a satin cloth prepared from acetate silk as warp and viscose crepe as weft are introduced at 40 C. into a dyebath which contains 001 gm. of 3:3:5:S-tetramethyloxa-cyanate ptoluene sulphonate and 1 gm. Glauber salts dissolved in 1000 cc. water. The dyebath is warmed during 15 minutes to 70 C. and then maintained at this temperature for a further 15 minutes. The cloth is then rinsed with cold water and dried. The treated material viewed in daylight appears uniformly brightened.

Example 3 20 gm. of acetate silk skein are introduced at 50 C. into a dyebath containing 0.01 gm. 3 :3 :5 :5-tetramethyloxacyanine p-toluene sulphonate in 1000 cc. of Water. The temperature is raised during 15 minutes to 80 C. and kept at this temperature for a further 15 minutes. The skein is then rinsed with cold water and dried. The yarn so obtained exhibits a very good brightened effect in daylight which is characterised by good light fastness and fastness to Washing.

Example 4 30 gm. of a satin cloth prepared from acetate silk as warp and viscose crepe as weft are introduced at 40 C. into a dyebath which contains 0.0025 gm. of 3:3-dimethyl-5:5-dimethoxy-oxacyanine p-toluene sulphonate and 1 gm. of Glauber salts dissolved in 1000 cc. of water. The dyebath is warmed during minutes to 70 C. and then maintained at this temperature for a further 15 minutes. The cloth is then rinsed with cold Water and dried. The treated material viewed in daylight appears uniformly brightened.

Example 5 gm. of acetate silk skein are introduced at 50 C. into a dyebath containing 0.005 gm. 3:3- dimethyl-5-methoXy-5'-methyloxacyanine p-tol uene sulphonate in 1000 cc. of water. The temperature is raised during 15 minutes to 80 C. and

kept at this temperature for a further 15 minutes. The skein is then rinsed with cold Water and dried. The yarn so obtained exhibits a very good brightened effect in daylight which is characterised by good light fastness and fastness to washing.

Though these examples refer to only five specific compounds, it is to be understood that any others of the compounds listed above may be substituted therefor with results which differ only in degree.

What we claim is:

1. Fibrous materials comprising fibres of organic derivatives of cellulose having adsorbed thereto a compound of the general formula:

where R1 and R2 are selected from the class consisting of alkyl and oxyalkyl groups and R3 to R10 inclusive are selected from the class consisting of hydrogen atoms, halogen atoms and alkyl, alkoxy, amino and substituted amino groups, and X is an acid radicle, which compound is colourless in ethyl alcoholic solution.

2. Fibrous materials comprising fibres of organic derivatives of cellulose having adsorbed thereto a compound of the general formula:

where R1 and R2 are selected from the class consisting of alkyl and oxyalkyl groups and R3 to R10 inclusive are selected from the class consisting of hydrogen atoms, halogen atoms and alkyl, alkoxy, amino and substituted amino groups, and X is an acid radicle, which compound is colourless in ethyl alcoholic solution.

4. Fibrous materials comprising cellulose ester fibres having adsorbed thereto an oxacyanine salt of which the benzene nuclei contain as sole substituents at most 2 lower alkyl groups.

5. Fibrous materials comprising cellulose ester fibres having adsorbed thereto an oxacyanine salt of which the benzene nuclei contain as sole substituents at most 2 methyl groups.

6. Fibrous materials comprising cellulose ester fibres having adsorbed thereto an oxacyanine salt of which the benzene nuclei contain as sole substituents at most one lower alkyl group and at most one lower alkoxy group.

7. Fibrous materials comprising cellulose ester fibres having adsorbed thereto an oxacyanine salt of which the benzene nuclei contain as sole substituents at most one methyl group and at most one methoxy group.

8. Fibrous materials of organic derivatives of cellulose having adsorbed thereto 3.3'.5.5'-tetramethyl oxacyanine p-toluene sulphonate.

9. Fibrous materials of organic derivatives of cellulose having adsorbed thereto 3.3'-dimethyl- 5.5'-dimethoxy-oxacyanine p-toluene sulphonate.

l0. Fibrous materials of organic derivatives of cellulose having adsorbed thereto 3.3-dimethyl- 5-methoxy-5'-methyl oxacyanine p-toluene sulphonate.

11. Cellulose acetate fibrous materials having adsorbed thereto 3.3'.5.5'-tetramethy1 oxacyanine p-toluene sulphonate.

12. Cellulose acetate fibrous materials having adsorbed thereto 3.3-dimethy1-5.5'-dimethoxyoxacyanine p-toluene sulphonate.

13. Cellulose acetate fibrous materials having adsorbed thereto 3.3-dimethy1-5-methoXy-5'- methyl oxacyanine p-toluene sulphonate.

JOHN DAVID KENDALL. DOUGLAS JAMES FRY.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,072,908 Schneider Mar. 9, 1937 2,108,485 Hamer Feb. 15, 1938 2,334,348 Miglorese Nov. 16, 1943 2,468,431 Eberhart Apr. 26, 1949 2,528,323 Thomas Oct. 31, 1950 FOREIGN PATENTS Number Country Date 522,672 Great Britain June 24, 1940 566,810 Great Britain Jan. 15, 1945 OTHER REFERENCES Geigy, Rayon Textile Monthly, September 1947, page 118.

Londolt, American Dyestufi Reporter, Apri1 18, 1949, pages 353356. 

1. FIBROUS MATERIALS COMPRISING FIBRES OF ORGANIC DERIVATIVES OF CELLULOSE HAVING ADSORBED THERETO A COMPOUND OF THE GENERAL FORMULA: 